1-(Triphenylphosphoranylidene)acetone → methylene-(2S,5R)-6-[(E)-acetonylidene]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate

HRID 1981201Notes

Reaction equation

HRID 1981201 reaction equation
[C:1]([OH:7])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].[CH2:8]=[S:9]1[CH:15]2[N:12]([C:13](=[O:17])[C:14]2=O)[CH:11]([C:18]([OH:20])=[O:19])[C:10]1([CH3:22])[CH3:21].C1(P(C2C=CC=CC=2)(C2C=CC=CC=2)=[CH:30][C:31](=[O:33])[CH3:32])C=CC=CC=1>C1C=CC=CC=1>[C:1]([OH:7])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].[CH2:8]=[S:9]1[C@H:15]2[N:12]([C:13](=[O:17])/[C:14]/2=[CH:30]\[C:31]([CH3:32])=[O:33])[C@@H:11]([C:18]([OH:20])=[O:19])[C:10]1([CH3:22])[CH3:21].[C:1]([OH:7])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].[CH2:8]=[S:9]1[C@H:15]2[N:12]([C:13](=[O:17])/[C:14]/2=[CH:30]/[C:31]([CH3:32])=[O:33])[C@@H:11]([C:18]([OH:20])=[O:19])[C:10]1([CH3:22])[CH3:21]

Participants

5

Reactant 2

HCID 150381-(Triphenylphosphoranylidene)acetoneHCID 86740043Methylene-6,7-dioxo-3,3-dimethyl-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate

Product 2

HCID 86740039methylene-(2S,5R)-6-[(E)-acetonylidene]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalateHCID 86740041methylene-(2S,5R)-6-[(Z)-acetonylidene]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A solution of 3.5 g of methylene-6,7-dioxo-3,3-dimethyl-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate in 150 ml of benzene is treated at room temperature with 6.3 g of 1-triphenylphosphoranylidene-2-propanone. After 10 minutes, the reaction mixture is evaporated. The residue is chromatographed on silica gel while eluting with cyclohexane/ethyl acetate (6:4). There are obtained methylene-(2S,5R)-6-[(E)-acetonylidene]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate [Rf: 0.47; cyclohexane/ethyl acetate (6:4); NMR (CDCl3), δ (ppm): 1.24 (9H); 1.52 (3H); 1.62 (3H); 2.62 (3H, Ac); 4.65 (1H3); 5.82 (1H5); 5.9 (m, 2H); 6.11 (1H)] and methylene-(2S,5R)-6-[(Z)-acetonylidene]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate [Rf: 0.53; cyclohexane/ethyl acetate (6:4); NMR (CDCl3), δ (ppm): 1.25 (9H); 1.53 (3H); 1.61 (3H); 2.38 (3H, Ac); 4.64 (1H3); 5.91 (m, 2H); 6.08 (1H5): 6.63 (1H)].

Workup

  1. customthe reaction mixture is evaporated
  2. customThe residue is chromatographed on silica gel
  3. washwhile eluting with cyclohexane/ethyl acetate (6:4)

Sources & evidence

ORD record
ord-f7cad5247b0147b09bd4db66908a8357
Source dataset
uspto-grants-1985_04
Patent number
US04512999

Reaction notes

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